Techniques for rapid detection and quantitation of volatile organic compounds (vocs) using breath samples

ABSTRACT

An exemplary breath analysis system may include a sampling chamber having a molecule collector disposed therein. The molecule detector may be configured such that volatile organic compounds (VOCs) present in a breath sample introduced to the sampling chamber adhere to the molecule collector. A heating element may introduce heat within the sampling chamber, causing release of at least a portion of the VOCs adhered to the molecule collector. An analysis device (e.g., a mass spectrometer or tetrahertz (THz) spectrometer) may identify one or more target VOCs from among at least the portion of the VOCs released from the molecule collector and generate an output representative of the identified one or more target VOCs. The output may include information that quantitates a concentration of the one or more target VOCs with respect to a source of the breath sample.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/715,576 filed Dec. 16, 2019, which is a 35 U.S.C. § 111(a)continuation of PCT Application No. PCT/M2019/056456, filed Jul. 29,2019, which claims the benefit of priority of U.S. Provisional PatentApplication No. 62/712,941, filed Jul. 31, 2018, the disclosures ofwhich are hereby incorporated by reference in their entirety.

TECHNICAL FIELD

The present application relates to breathalyzer systems and devices.More specifically the present application relates to breathalyzersystems and devices designed to facilitate quantitative analysis of THCand other substances in the field using breath samples.

BACKGROUND

Marijuana legalization has created many judicial issues and raisesconcerns of safety for civilians. Daily marijuana users have increasedfrom 9.8% of the population of the United States in 2007, to 13.39% in2014. While this is only a 3.6% increase, the potency ofΔ-9-Tetrahydrocannabinol (Δ-9-THC), the psychoactive substance inmarijuana, has also increased from 5% in 2001 to over 20% in marijuanaleaves and over 60% in crude extracts. The increase in potency has ledto an increase in crime reports for the local population. Specifically,areas with a high density of marijuana dispensaries had higher rates ofproperty crime among all states with dispensaries. Another problem withmarijuana legalization is the influence of marijuana while operating anautomobile. Marijuana users are 25% more likely to be in an automobileaccident than a sober driver, and more than 10% of all drivers on theweekend are under the influence of an illegal drug. As marijuana becomeslegalized in more states, proper quantitation of Δ-9-THC is required,such that an accurate and rapid determination of whether a person isunder the influence of marijuana can be achieved. This will also aid thejudicial system in having a device that can accurately determine aconcentration, allowing a set limit of Δ-9-THC to be determined foroperating a vehicle.

Three cannabinoid compounds are currently analyzed to determinecannabinoid concentrations in the blood; they are Δ-9-THC,11-hydroxy-tetrahydrocannabinol (11-OH-THC), andcarboxy-tetrahydrocannabinol (THC-COOH). Currently, techniques fordetermining the presence of drugs, such as cannabinoids, requireanalysis via a blood, blood plasma, urine, or oral fluid samples. Mostanalytical techniques use gas chromatography coupled to massspectrometry (GC/MS). This presents a problem of having to collect asample and bring it back to the lab for further analysis. Thesetechniques have a long analysis time, with most analyses taking morethan 15 minutes to detect the cannabinoids. Furthermore, detectingΔ-9-THC using GC/MS can also introduce another problem because theionization source is electron ionization (EI). Cannabidiol (CBD), anextracted resin from the hemp plant, has the same molecular weight asΔ-9-THC, as well as the same mass spectrum fragmentation patterns whenionized using electron ionization. Under the controlled substances act,CBD is classified as a Schedule I drug because of it being a derivativeof marijuana. However, the agricultural act of 2014 allows industrialhemp to be cultivated and sold for purposes of marketing research. Somestates view this bill as the right to contract agriculturalists to sellCBD legally. This creates a challenge in quantifying the amount ofΔ-9-THC in person's breath because the signal may be a result of CBD inthe person's breath, which they may have obtained legally.

Laws for legal limits of Δ-9-THC in the body have been established insome states. Twelve states have the zero-tolerance policy, which statesthat no person should have any cannabinoids their blood while driving.However, five states allow the use of medical marijuana. This causes anissue for patients getting treatment and then having to drive later inthe day or later in the week because they could be considered to drivingunder the influence of marijuana (DUIM). The analytical techniques thattest for all three cannabinoids can be problematic because THC-COOH,which is not psychoactive, remains in the blood long after both Δ-9-THCand 11-OH-THC remain in the blood. A person can fail a cannabinoid testeven though they are experiencing no psychoactive effects. Other stateshave adopted per se blood cannabis content (BCC) laws. These selectstates each have their own limit with the overall range being between 1nanogram of THC to milliliter of blood (ng/ml) to 5 ng/ml. If the persondriving has a concentration higher than those values, they are deemedDUIM, which carries similar penalties to driving while intoxicated.Unfortunately, a device that can accurately and rapidly detect Δ-9-THCconcentrations has yet to be developed.

Detecting cannabinoids from the breath of a person is needed to allow anon-invasive rapid determination in the field. Previous methods ofbreath determination of cannabinoids originate back to 1972, whenmarijuana was detected in the breath of people under the influence usinga colorimetric test. This test collected breath and used a series ofreactions with quinone-4-haloimine, 2,6-dihaloquinone-4-haloimine,sodium hydroxide, and ammonia to determine if the breath sample wouldchange to a blue or red color. These colorimetric tests had to be donein large reaction vessels, had a broad range of colors representing apositive result, and required at least 1 microgram of THC in the breathto have a positive reaction. These tests were not capable ofquantitating the level of Δ-9-THC, nor were they able to be used in thefield.

Currently, three types of breathalyzers are being used by local lawenforcement officers in the field, liquid chromatography coupled to massspectrometry (LC/MS), high-field asymmetric waveform ion mobility(FAIMS), and liquid chromatography coupled to spectroscopy. A firstcompany, Sensabues, utilizes a breath sampling kit. The person breathesinto the sampling chamber and then the apparatus is sent back to the labto be analyzed using LC/MS. While this method is useful forquantitation, it cannot be used in the field, which hinders this method.In addition, LCMS requires several minutes to analyze the sample once ithas reached the lab before the cannabinoids can be seen. Two othercompanies provide systems that are capable of in field measurements.Cannabix Technologies Inc. has worked with the Yost research group atUniversity of Florida to create a portable breathalyzer for Δ-9-THC thatutilizes high-field asymmetric waveform ion mobility spectrometry(FAIMS). This device can analyze samples in a two-minute time window andcan detect and quantitate Δ-9-THC in the sample at concentrations of 10parts per million (ppm). While this device overcomes the portabilityissue, FAIMS does not contain the same resolution or peak capacity thatis necessary for determining the concentration of Δ-9-THC. Without theproper resolution, the instrument would not be able to distinguish thecompounds of tobacco smoke from cannabis smoke. Furthermore, without thepeak capacity, other compounds, such as illicit drugs may be overlooked,allowing the driver to continue driving while under the influence of adifferent illicit substance. Another company, Hound Labs Inc., hasdeveloped a handheld instrument that also utilizes liquid chromatographycoupled to spectroscopy to detect for the presence of Δ-9-THC by linkinga fluorescent adduct to the para-position of the Δ-9-THC molecule. Thisdevice only requires picogram quantities of Δ-9-THC and works bycapturing the breath of the person and condensing the breath onto C18media. The media is then delivered to a TLC plate, where a solventmixture is administered and after several minutes the fluorescent labelis placed on the entire TLC plate. The fluorescent label will bindspecifically to the Δ-9-THC, which is then excited using a diode-pumpedsolid-state laser. This excited state will cause a shift in the spectrumand can be referenced to a known Δ-9-THC sample. This method requiresmore than 8 minutes to analyze a sample and requires the use of a knownreference every time an analysis takes place.

Since the turn of the century the number of synthetic opioid overdosesof civilians have risen 200% and from the years 2014-2016 50% of alldrug overdoses were attributed to opioids. Military personnel have alsohad an increase in opioid overdoses as military emergency departmentshave recorded a steady rise of opioid overdoses increasing from 27% to42% during the years of 2009-2012. With so many opioid overdosesoccurring among both civilians and military personnel a need forimproved detection methods is warranted. Most drug enforcement agenciescan only analyze the opioid using gas chromatography coupled to massspectrometry (GC/MS) or liquid chromatography to mass spectrometry(LC/MS). Opioids such as methadone and fentanyl are immediatelyhydroxylated upon entering the human body. This process of hydroxylationbegins a metabolic cycle that creates volatile organic compounds (VOCs)such as propionic acid. Previous methods used to detect these VOCs havebeen with solid phase micro extraction (SPME) techniques coupled toGC/MS. Unfortunately, these methods require long equilibration times ofup to 10 minutes.

SUMMARY

Systems, apparatuses, methods, and computer-readable storage mediaproviding techniques for improved on-site quantitation of cannabinoidsand other substances from breath samples are disclosed. Exemplary breathanalysis systems and apparatuses of the present disclosure may include asampling chamber having an inlet configured to receive a breath sampleand provide the breath sample to the sampling chamber. A moleculecollector may be disposed within the sampling chamber. The moleculedetector may be configured such that volatile organic compounds (VOCs)present in the breath sample introduced to the sampling chamber adhereto the molecule collector. The breath analysis systems and apparatusesmay include a heating element configured to introduce or induce heatwithin the sampling chamber, which may cause resorption of at least aportion of the VOCs adhered to the molecule collector. The exemplarybreath analysis systems and apparatuses may include an analysis deviceconfigured to identify one or more target VOCs from among at least theportion of the VOCs released from the molecule collector and generate anoutput representative of the identified one or more target VOCs. Theoutput may include information that quantitates a concentration of theone or more target VOCs with respect to a source of the breath samplewith respect to the breath sample provided to the sampling chamber. Inaspects, the analysis device may identify the one or more target VOCsusing a mass spectrometer or tetrahertz (THz) spectrometer.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter which form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand specific embodiment disclosed may be readily utilized as a basis formodifying or designing other structures for carrying out the samepurposes of the present invention. It should also be realized by thoseskilled in the art that such equivalent constructions do not depart fromthe spirit and scope of the invention as set forth in the appendedclaims. The novel features which are believed to be characteristic ofthe invention, both as to its organization and method of operation,together with further objects and advantages will be better understoodfrom the following description when considered in connection with theaccompanying figures. It is to be expressly understood, however, thateach of the figures is provided for the purpose of illustration anddescription only and is not intended as a definition of the limits ofthe present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, reference isnow made to the following descriptions taken in conjunction with theaccompanying drawings, in which:

FIG. 1 illustrates a block diagram of a system for analyzing breathsamples in accordance with aspects of the present disclosure;

FIG. 2 illustrates a diagram of a mass spectrometer-based system foranalyzing breath samples in accordance with aspects of the presentdisclosure;

FIG. 3 illustrates a diagram of a Terahertz spectrometer-based systemfor analyzing breath samples in accordance with aspects of the presentdisclosure;

FIG. 4A is a diagram illustrating aspects of receiving a breath samplein a system configured in accordance with aspects of the presentdisclosure;

FIG. 4B is a diagram illustrating aspects the behavior of breath samplemolecules received in a system configured in accordance with aspects ofthe present disclosure;

FIG. 4C is a diagram illustrating aspects of analyzing breath samplemolecules using a mass spectrometer-based system configured inaccordance with aspects of the present disclosure;

FIG. 4D is a diagram illustrating aspects of analyzing breath samplemolecules using a Terahertz (THz) spectrometer-based system configuredin accordance with aspects of the present disclosure;

FIG. 5 is a graph illustrating observed VOCs for a healthy breathsample;

FIG. 6 is a graph illustrating observed VOCs for a breath sample of aperson suffering from seasonal allergies;

FIG. 7 is a graph illustrating observed VOCs for a breath sample of aperson after using mouthwash;

FIG. 8 is a graph illustrating observed VOCs for toluene, benzene, andxylene;

FIG. 9 is a graph illustrating observed VOCs for a marijuana sample; and

FIG. 10 is a flow diagram of a method for analyzing a breath sample inaccordance with aspects of the present disclosure.

DETAILED DESCRIPTION

Various features and advantageous details are explained more fully withreference to the non-limiting embodiments that are illustrated in theaccompanying drawings and detailed in the following description.Descriptions of well-known starting materials, processing techniques,components, and equipment are omitted so as not to unnecessarily obscurethe invention in detail. It should be understood, however, that thedetailed description and the specific examples, while indicatingembodiments of the invention, are given by way of illustration only, andnot by way of limitation. Various substitutions, modifications,additions, and/or rearrangements within the spirit and/or scope of theunderlying inventive concept will become apparent to those skilled inthe art from this disclosure.

Referring to FIG. 1, a block diagram of a system for analyzing breathsamples in accordance with aspects of the present disclosure is shown asa system 100. As shown in FIG. 1, the system 100 includes a samplingchamber 110 and an analysis device 120. In aspects, the sampling chamber110 may be configured as a removable and/or disposable component of thesystem 100. In such an arrangement, the sampling chamber 110 may beremovably coupled to the analysis device 120. Configuring the samplingchamber 110 as a removable component of the system 100 may preventcontamination of consecutive breath samples analyzed by the analysisdevice 120. For example, a first sampling chamber may be utilized toperform analysis of a breath sample provided by a first person and asecond sampling chamber may be utilized to perform analysis of a breathsample provided by a second person. Using different sampling chambersfor different breath samples prevents one breath sample from potentiallycontaminating another breath sample. Where the sampling chamber(s) 110is configured as a disposable component, the sampling chamber may bediscarded after use or after a desired time has elapsed, such as anamount of time required by a law enforcement agency to retain thesampling chamber (e.g., for evidentiary purposes). Where the samplingchamber(s) 110 is configured as a reusable component, the samplingchamber 110 may be cleaned and prepared for subsequent reuse as needed.In aspects, a portion of the analysis device 120 may also be configuredas a disposable and/or reusable component, such as portions of theanalysis device 120 that may become contaminated if utilized to analyzemultiple breath samples. In an aspect, the sampling chamber may beconfigured as a cartridge that may be utilized to obtain a breath sampleand then placed within or coupled to the sampling device 120 foranalysis. For example, the analysis device 120 may be installed in a lawenforcement vehicle and a law enforcement official may have a personsuspected of DUIM provide a breath sample to the cartridge, and thencouple the cartridge to the analysis device 120 to facilitate analysisin accordance with aspect of the present disclosure. It is noted thatthe exemplary configurations described above have been provided forpurposes of illustration, rather than by way of limitation and thatnumerous other ways for arranging, coupling, and/or integratingcomponents of breath analysis systems in accordance with the presentdisclosure may be utilized.

As shown in FIG. 1, the sampling chamber 110 may comprise a housinghaving an outer surface 104 and an inner surface 106. The inner surface106 of the housing may define a volume of the sampling chamber. An inlet112 may be coupled to the sampling chamber 110. The inlet 112 may beconfigured to receive a breath sample 102 and to provide the breathsample 102 to the sampling chamber 110, and more specifically to providethe breath sample 102 to the volume of the sampling chamber. In aspects,a disposable mouthpiece (not shown in FIG. 1) may be removably coupledto a first end of the inlet 112 and a second end of the inlet 112 may becoupled to the sampling chamber 110. Alternatively, the first end of theinlet 112 may be utilized as the mouthpiece and the second end of theinlet 112 may be coupled to the sampling chamber 110. A valve 113 may bedisposed within an air flow path between the inlet 112 and the samplingchamber 110. The valve 112 may be configurable to at least a first stateand a second state. The first state may correspond to an open stateconfigured to allow the breath sample 102 to flow into the samplingchamber 110 and the second state may correspond to a closed stateconfigured to prevent contamination of the breath sample 102, such as bypreventing ambient air from entering the sampling chamber 110 once thebreath sample 102 has been provided. In an aspect, the sampling chamber110 may include an outlet configured to release non-VOCs from thesampling chamber 110, as illustrated and described below with referenceto FIG. 4A. The system 100 may also include a sensor 115 configured todetermine whether the breath sample satisfies one or more criterion. Forexample, the sensor 115 may be configured to determine whether thebreath sample 102 was exerted with sufficient force, has sufficientvolume, etc., which may ensure that the breath sample 102 is sufficientfor facilitating analysis in accordance with aspects of the presentdisclosure.

A molecule collector 116 may disposed within the sampling chamber 110.At least a portion of the molecule collector 116 may be disposed withinthe volume of the sampling chamber 110. The molecule collector 116 maybe configured to adhere to volatile organic compounds (VOCs) present inthe breath sample. For example, the molecule collector 116 may beconstructed of materials such as Carboxen®. It is noted that themolecule collector 116 may be formed from a single material (e.g., oneof the above-described materials), or may be formed from multiplematerials, such as a base material that has been coated with one or moreof the above-described materials. In aspects, the molecule collector 116may have a solid form factor, such as a plate or rod formed from thematerials mentioned above, or may have another form factor, such as amesh formed from the materials mentioned above. The sampling device 110may also include or be coupled to a heating element 118 configured tointroduce heat within the sampling chamber 110. For example, the heatingelement 118 may include a power source coupled to the molecule collector116 and configured to apply a voltage to the molecule collector 116.Applying the voltage to the molecule collector 116 may heat up themolecule collector, thereby introducing heat within the sampling chamber110. As described in more detail below, the heat introduced within thesampling chamber 110 may cause the VOCs adhered to the moleculecollector 116 to be released within the volume of the sampling chamber,thereby facilitating analysis and identification of one or more of theVOCs present within the sampling chamber 110.

The system 100 may include an analysis device. The analysis device 120may be configured to identify one or more target VOCs from among theVOCs present in the sampling chamber 110 subsequent to release of atleast a portion of the VOCs from the molecule collector 116 (e.g., dueto the heat provided or introduced by the heating element 118).Additionally, the analysis device 120 may be configured to generate anoutput representative of the one or more target VOCs. As shown in FIG.1, the analysis device 120 may include one or more processors 122, amemory 130, analysis components 124, and one or more input/output (I/O)devices 126. The memory 130 may store instructions 132 that, whenexecuted by the one or more processors 122, cause the one or moreprocessors 122 to control operations of the analysis device 120 andpossibly other components of the system 100, such as the heating element118, with respect to analyzing and identifying one or more target VOCsof the breath sample 102. The one or more target VOCs may includeΔ-9-Tetrahydrocannabinol (Δ-9-THC), THC metabolites, opioids, opioidmetabolites, or a combination thereof.

The I/O devices 126 may include switches, buttons, lights, displaydevices, or other control elements configured to receive inputs and/orprovide outputs in connection with operation of the system 100. Forexample, switches and/or buttons may be provided to power the system 100on and off, indicate that a breath sample has been provided, identifyone or more target VOCs to be identified, or other functionality andcontrol features. Lights may be provided to indicate: the system 100 ispowered on or off, indicate whether the breath sample provided issatisfactory (e.g., based on information received from the sensor 115),indicate the identified VOCs (e.g., different lights may be associatedwith different VOCs that may be identified by the system 100), or toprovide other information associated with operation of the system 100.One or more display devices may additionally be provided to displayinformation, such as to indicate the identified VOCs, indicate anoperational state of the system 100 (e.g., provide informationindicating one or more of the different features described above withrespect to the lights or other status information), and the like. Theanalysis component 124 may include a mass spectrometer or a tetrahertz(THz) spectrometer configured to identify the one or more target VOCs ofthe breath sample 102.

Referring to FIG. 2, exemplary aspects of a system 100 utilizing massspectrometer-based analysis components are illustrated. It is noted thatin FIGS. 1 and 2, like reference numbers are utilized to refer tosimilar components. As shown in FIG. 2, the analysis components 124 mayinclude an ionizer 222, a mass analyzer 224, and a detector 226. Asdescribed above, a breath sample 102 may be provided to the inlet 112via a mouthpiece 210 when the valve 113 is in an open state. Subsequentto the breath sample 102 being provided to the volume of the samplingchamber 110, the heating element 118 (not shown in FIG. 2) may beactivated, causing resorption of the VOCs adhered to the moleculecollector 116. An outlet 204 may be utilized to provide the releasedVOCs to the analysis components 124. A valve 213 may be configurable toa first state (e.g., an open state) and a second state (e.g., a closedstate) to control the providing of the VOCs to the analysis components.For example, in the first state, the VOCs may be allowed to pass throughthe outlet 204 to the analysis components 124 and in the second state,the VOCs may be prevented from passing through the outlet 204 to theanalysis components 124. The ionizer 222 may be configured to ionize atleast the portion of the VOCs released from the molecule collector toproduce one or more ionized fragments. The mass analyzer 224 may beconfigured to separate the one or more ionized fragments (e.g.,according to a mass-to-charge ratio of the one or more ionizedfragments) and the detector 226 may be configured to identify the one ormore target VOCs based on the separated one or more ionized fragments.In an aspect, the mass spectrometer components (e.g., the ionizer 222,the mass analyzer 224, and the detector 226) may operate under controlof, or in coordination with, a computing device, such as a computingdevice that includes the one or more processors 122, the memory 130, andthe one or more I/O devices 126. For example, the computing device mayreceive information from the mass spectrometer components, such asinformation associated with the one or more target VOCs identified inthe breath sample 102, and may generate the output representative of theone or more target VOCs based on information associated with the one ormore target VOCs. Additionally, the computing device may be configuredto display the output at an output device, such as a display device.

Referring to FIG. 3, exemplary aspects of a system 100 utilizing THzspectrometer-based analysis components is illustrated. It is noted thatin FIGS. 1 and 3, like reference numbers are utilized to refer tosimilar components. As shown in FIG. 2, the analysis components 124 mayinclude an excitation source 320 and a detector 322. As described above,a breath sample 102 may be provided to the inlet 112 via a mouthpiece310 when the valve 113 is in an open state. Subsequent to the breathsample 102 being provided to the volume of the sampling chamber 110, theheating element 118 (not shown in FIG. 3) may be activated, causingresorption of the VOCs adhered to the molecule collector 116. Theexcitation source 320 may be configured to introduce an excitationsignal 324 within the sampling chamber subsequent to the release of atleast a portion of the VOCs from the molecule collector 116 and thedetector 322 may be configured to identify the one or more target VOCsbased on one or more characteristics associated with excitation of atleast the portion of the VOCs released from the molecule collector 116in response to the excitation signal 324. In an aspect, the excitationsource 320 may be a THz laser device and the excitation signal 324 maybe a THz laser signal. In aspects, the one or more characteristicsassociated with the excitation of at least the portion of the VOCs mayinclude at least one of an absorbance characteristic and a fluorescentemission characteristic, which may be utilized to identify the one ormore target VOCs present within the breath sample 102, as described inmore detail below. In an aspect, the THz spectrometer components (e.g.,the excitation source 320 and the detector 322) may operate undercontrol of, or in coordination with, a computing device, such as acomputing device that includes the one or more processors 122, thememory 130, and the one or more I/O devices 126. For example, thecomputing device may receive information from the THz spectrometercomponents, such as information associated with the one or more targetVOCs identified in the breath sample 102, and may generate the outputrepresentative of the one or more target VOCs based on informationassociated with the one or more target VOCs. Additionally, the computingdevice may be configured to display the output at an output device, suchas a display device.

Referring back to FIG. 1, the output representative of the one or moretarget VOCs may include information that quantitates a concentration ofthe one or more target VOCs with respect to a source of the breathsample. This information may facilitate a determination of whether asource of the breath sample, such as a person that provided the breathsample 102, is impaired or under the influence of one or more substances(e.g., substances corresponding to the identified one or more targetVOCs). By providing information that quantitates the concentration ofthe one or more target VOCs, more accurate determinations of whether thesource is impaired or under the influence of substances may bedetermined. Additionally, the techniques utilized by the system 100 (asconfigured in accordance with either FIG. 2 or FIG. 3) may facilitatemore rapid identification and quantitation of the VOC levels, therebyfacilitating in field determinations as to whether source is impaired orunder the influence of one or more substances, such as THC. For example,unlike existing systems capable of quantitatively analyzing certainVOCs, which take a long time to complete, the system 100 may facilitatedetermination and quantization of VOCs in a few seconds, therebyfacilitating practical use in the field, such as by law enforcementofficials.

Referring to FIGS. 4A-4D, various aspects of systems for analyzing VOCspresent in breath samples in accordance with aspects of the presentdisclosure are shown. As shown in FIG. 4A, a breath sample may beprovided to the sampling chamber 110 via the inlet 112. The breathsample may include one or more VOCs, such as the exemplary VOCs 404,406, 408 shown in FIG. 4A. Additionally, the breath sample may includenon-VOCs, which may include other gases, such as CO₂ 402. In an aspect,the sampling chamber 110 may include an outlet 410 configured to releasenon-VOCs from the sampling chamber 110. It is noted that the outlet 410is not the same as the outlet 204 of FIG. 2. As shown in FIG. 4B, theVOCs 404, 406, 408 present in the breath sample may adhere to themolecule collector 116. In FIG. 4C, the heating element 118 (not shownin FIGS. 4A-4D) has been activated, introducing heat within the samplingchamber 110, which causes the VOCs to release from the moleculecollector 116. After the VOCs are released from the molecule collector116, the VOCs (or at least a portion of the VOCs) may be provided to amass spectrometer-based analysis device, such as the analysis deviceillustrated in FIG. 2, via outlet 204 (not shown in FIG. 4C), foranalysis, as described above with reference to FIG. 2. In FIG. 4D, theheating element 118 (not shown in FIGS. 4A-4D) has been activated,introducing heat within the sampling chamber 110, which causes the VOCsto release from the molecule collector 116. After the VOCs are releasedfrom the molecule collector 116, the VOCs (or at least a portion of theVOCs) may be provided to a THz spectrometer-based analysis device, suchas the analysis device illustrated in FIG. 3, for analysis, as describedabove with reference to FIG. 2. For example, as illustrated in FIG. 4D,the excitation signal 324 may be provided or projected within thesampling chamber. As described below, excitation of the VOCs by theexcitation signal 324 may be utilized by the detector 322 to identifyone or more target VOCs present in the breath sample provided tosampling chamber 110.

It is noted that THz spectrometer based systems may provide severaladvantages over existing systems. For example, using a THz spectrometermay facilitate rapid analysis of breath samples, which may be completedin a matter of seconds, and may facilitate a portable system that can betransported in a local law enforcement vehicle. Additionally, THzspectroscopy-based systems are able to differentiate between Δ-9-THC andCBD because the bonds in the molecules are different. THz spectroscopyor far-infrared spectroscopy may be used to identify compounds that havedipoles that contain a rotational motion. The spectroscopic range isin-between the microwave and infrared region operating at is between 3mm-30 μm or 0.1-10 THz. Another advantageous aspect of THzspectrometer-based systems is the granularity at which compounds, suchas VOCs, may be identified. For example, THz time domain spectroscopy(THz-TDS) is capable of detecting compounds with concentrations as lowas parts-per-trillion. THz-TDS works by emitting a pulsed femtosecondlaser, which may be a Ti:Sapphire laser. The laser is sent to twophotoconductive antennas after being split in a delay line, resulting aprobe beam and a pump beam. The pump beams excites a non-linear crystal,which may formed from gallium arsenide (GaAs), and focuses the signal tothe sampling space, such as the volume within the sampling chamber 110.The probe beam sends a signal to the second photoconductive antenna,which detects the THz radiation. To obtain a spectrum of a sample ablank must be taken before the sample, which acts as a reference tosubtract from the THz spectra of the sample. THz-TDS is useful indetermining the torsional deformations of molecules and theintermolecular bonding of molecules. The benefit of analyzing a gasphase compound, such as breath, is that intermolecular bondinginteractions are weaker in the gas phase, leaving only the torsional androtational spectroscopy signal. One challenge faced by THz-TDS for gasanalysis is the large presence of water in the atmosphere, which mayalter the device's accuracy depending on the altitude of the device.This issue may be overcome by the collection of background beforeanalysis and with the use of a vacuum or a dry inert gas, such ashelium, which removes the water in the signal.

The signal of cannabinoids in the breath may be too low for detectionvia THZ-TDS, however a pre-concentrator may be used to achieve asuitable signal. Previously, pre-concentration devices have beenutilized in the analysis of Δ-9-THC using LC/MS. However, thosepre-concentration devices utilized sorbent trapping materials whichretain water and impair identification of volatile organic compounds(VOCs). To overcome this challenge, the molecule collector 116 describedabove may utilize carbon molecular sieves, which reduce the amount ofwater uptake when looking for VOCs. Carbon molecular sieves work bytrapping the compound between graphitic planes, allowing molecules todiffuse fast or slow based on the size of the molecule. The moleculescan be rapidly emitted when a heating element is applied to the sorbentmaterial as the graphitic planes enlarge. As described above, in thesystems of the present disclosure, a conductive material formed from orcoated with a carbon molecular sieve sorbent material may be used as themolecule collector. Based on the type of sorbent material, however, thematerial may release the VOCs at a different rate, allowing a separationto still be achieved. This process of desorption distinguishes certaincarbon molecular sieves materials from others in rapid gas analysistechniques. In aspects, the molecule collector 116 may be formed form aVOC desorptive material, such as Carboxen® (e.g., Carboxen® 1000).Carboxen® may be used in rapid VOC gas analysis to identify specificmolecules based on emission time. Larger molecules may not be emittedfrom the graphitic plane faster than the smaller molecules, allowing thesmaller compounds to desorb and be analyzed faster than the largermolecules.

In the description that follows, a THz spectroscopy-based system forcannabinoid detection similar to the system described above withreference to FIG. 3, was cross-referenced with a Thermo Fischer PolarisQmass spectrometer-based system similar to the system described abovewith reference to FIG. 2. In the experimental setup, a sampling chambercontaining a molecule collector formed from a Carboxen® 1000 coated meshwas coupled to a heating element (e.g., a 24-volt power supply). With avalve connecting an inlet and replaceable mouthpiece to the samplingchamber open, a person would exhale a breath into the sampling chamber,trapping the VOCs on the Carboxen® molecule collector. Other VOCs alsoadhered to the molecule collector, while non-VOC gases flowed over andout of the sampling tube (FIG. 4A). After completion of the exhale, thevalve was closed to prevent any extraneous compounds from depositingonto the molecule collector (FIG. 4B). The molecule collector was thensupplied with 24 volts to evenly heat the molecule collector and promoterapid desorption of the compounds adhered thereto. For mass spectrometryreference characterization, the released compounds were provided to themass spectrometer for a signal to be detected (FIG. 4C). Being formedfrom Carboxen®, the molecule collector also facilitated a separationtechnique, where smaller VOCs were emitted faster than larger compounds.This enabled a determination of the proper time at which thecannabinoids were emitted from the molecule collector. Once the propertime was determined, the THz spectrometer was used to determine thepresence of cannabinoids without the presence of other backgroundsignals, aiding in an accurate and precise measurement. Once this timereference of cannabinoids was collected, the sampling chamber was placedin the THz spectrometer-based analysis device, allowing the excitationsignal (e.g., a THz laser signal) to be used to detect the samplesemitted by the molecule collector (FIG. 4D). The THz spectrometer-basedsystem may act in two manners. The first being that the compounds (e.g.,the VOCs) may be emitted from the molecule collector and then be excitedvia the excitation signal. The excited molecule(s) may then be detectedas an absorbance by the detector as it returns to ground state. Theother mechanism would be that excitation of the molecule(s) due to therapid heating of the molecule collector may result in a fluorescentsignal being emitted. The system may be configured to determine thepresence of cannabinoids and/or other VOCs in the breath sample based onthe fluorescent signal emitted in response to the excitation of the VOCsby the excitation signal.

A mass spectrometer-based system was developed and utilized to analyzebreath samples. Using this system, differences in the physical state ofa person exhaling have already been demonstrated. Healthy breathsamples, breath samples from a person suffering from seasonal allergies(allergy breath), and breath samples obtained from a person directlyafter washing their mouth out with Listerine were collected in samplingchambers having a molecule collector formed from a Carboxen® coated meshattached to a PolarisQ ion trap mass spectrometer. The results of theanalysis performed on each of the breath samples are illustrated in FIG.5 (healthy breath sample), FIG. 6 (breath sample of a person sufferingfrom seasonal allergies), and FIG. 7 (breath sample from a persondirectly after washing with Listerine). In FIG. 5, cutout 504illustrates an enlarged view of the peaks illustrated in box 502. InFIG. 6, cutout 604 illustrates an enlarged view of the peaks illustratedin box 602. In FIG. 7, cutout 704 illustrates an enlarged view of thepeaks illustrated in box 702. As shown in FIG. 5, a large 51.93 m/zvalue was observed, which corresponds to 1-buten-3-yne. This1-buten-3-yne was not found in the allergy breath sample. In the allergybreath sample, the largest peak was observed at 66.93 m/z, whichcorresponds to isoprene, followed by peaks at 80.93 m/s(1-methyl-pyrrole) and 94.93 m/z (2-ethylpyrrole), as shown in FIG. 6.In the mouthwash sample, illustrated in FIG. 7, the peak associated withisoprene was lowered, as expected, and other peaks were established,such as the ethylmethylsulfide peak at 76.93 m/z and 1,2,3-propanetriolat 90.93 m/z. Furthermore, larger molecular weight compounds becamepresent, such as the octadecane peak at 254.60 m/z, illustrated incutout 604. The samples all show a prominent 66.93 m/z peak, whichdenotes isoprene. Isoprene should be found in all breath samples and maybe used as a reference to ensure that the instrument is sampling thebreath VOCs. As shown in FIGS. 5-7, prominent changes in the observedcompounds were be found in the three different scenarios presented.Utilizing this instrument as a reference, determination of cannabinoidsin breath samples was achieved using the terahertz spectrometer, asdescribed below.

The terahertz spectra of benzene, toluene, and xylene were acquired andcompared to the terahertz spectra of a gas sample of heated marijuanaleaves using a MenloSystems (Martinsried, Germany) K15 Time DomainTerahertz Spectrometer. This instrument was used to pump a dry gas,Helium, into a flask, forcing the volatile vapors out and into thesampling chamber where the VOCs adhered to a Carboxen®-based moleculecollector. A voltage was then applied to the molecule collector,releasing the VOCs. The results observed for benzene, toluene, andxylene are illustrated in FIG. 8, where lines 802 represent VOCsresulting from xylene, lines 804 represent VOCs resulting from toluene,and lines 806 represent VOCs from benzene. FIG. 9 illustrates VOCsobserved from the marijuana sample. The analysis of the gaseous samplesallowed the rotational spectroscopy to be obtained, explaining the lowsignal obtained for benzene at any of the frequencies scanned. Themarijuana sample resulted in the most number of rotational bonds, whichis to be expected as it was not a pure sample. The xylene and tolueneappeared to be the same peak, however the xylene consistently resultedin a lower frequency peak, while the toluene appeared at a higherfrequency. This is because xylene has two methyl groups attached to thearomatic ring, while the toluene only has one methyl group attached tothe aromatic ring.

Methods to quantitate gas based on terahertz spectra have been doneusing cigarette smoke using continuous wave terahertz spectroscopy.However, to do so a database to input variables for the Lorentzian fitequation is required. Cannabinoids have not yet been databased,preventing the Lorentzian fit equation from being useful in cannabinoidquantitation. However, quantitation can still be achieved using theabsorbance coefficient of the terahertz spectra. Based on thetransmission of the sample THz field compared to the transmission fieldthe measured transmission t(f), the absorbance coefficient can becalculated as:

$\begin{matrix}{{{n_{S}(f)} = {1 - \frac{c\; \varphi \; (f)}{2\pi \; {fd}}}},} & (1)\end{matrix}$

were ns(f) is the sample refractive index, c us the speed of light in avacuum, ϕ(f) is the phase difference between the transmission of thesample terahertz field and the transmission of the reference terahertzfield, f is the frequency, and d is the sample thickness. The samplethickness may be the length of the sampling chamber, which was 9 cm inthe above-described examples. The sample refractive index, expressed as:

$\begin{matrix}{{{\alpha (f)} = {{- \frac{2}{d}}\ln \frac{{t(f)}}{RL}}},} & (2) \\{{{RL} = \frac{4n_{s}}{\left( {1 + n_{s}} \right)^{2}}},} & (3)\end{matrix}$

may be calculated the absorption coefficient α(f) can be calculated,where the loss of signal at the interface is equal to RL. Subtractingthe sample spectra from the reference spectra allows the Beer-Lambertlaw to be used as follows:

$\begin{matrix}{{{\alpha (f)} = {- \frac{\ln \; {T(f)}}{d}}},} & (4)\end{matrix}$

where T(f) is equal to the ratio between the intensity of the sampletransmitted THz field and the reference transmitted THz field. This mayallow for a rapid quantitation of Δ-9-THC. A breath sample analyzersystem in accordance with the present disclosure may be configured(e.g., via software stored as instructions) to utilize these equationsto calculate the concentration of cannabinoids from the breath of theperson. The sample volume may change from person to person. Accordingly,the system may be configured to take the overall volume of the breathsample that the person has exhaled into consideration so as to avoid ormitigate inaccuracies in the determined concentration.

Referring to FIG. 10, a flow diagram of a method for analyzing a breathsample in accordance with aspects of the present disclosure is shown asa method 1000. In an aspect, the method 1000 may be performed by thesystem 100 of FIG. 1, which may utilize a mass spectrometer-basedapproach, as described above with reference to FIG. 2 or a THzspectrometer-based approach, as described above with reference to FIG.3. In an aspect, operations or steps of the method 100 may be realizedas a program or instructions (e.g., the instructions 132 of FIGS. 1-3)stored at a memory (e.g., the memory 130 of FIGS. 1-3) that, whenexecuted by one or more processors (e.g., the one or more processors 122of FIG. 1-3), cause the one or more processors to perform operations foranalyzing a breath sample in accordance with aspects of the presentdisclosure.

As shown in FIG. 10, the method 1000 includes, at step 1010, receiving,at a sampling chamber, a breath sample. As described above, the breathsample may be received at the sampling chamber via an inlet (e.g., theinlet 112 of FIG. 1) coupled to the sampling chamber (e.g., the samplingchamber 110 of FIG. 1) and the sampling chamber may include a moleculecollector (e.g., the molecule collector 116 of FIG. 1) disposed withinthe sampling chamber. At step 1020, the method 1000 includesintroducing, via a heating element, heat within the sampling chamber. Inan aspect, the heat may be introduced by the heating element 118 ofFIG. 1. At step 1030, the method 1000 includes identifying, by ananalysis device, one or more target VOCs from among the VOCs present inthe sampling chamber subsequent to release of at least a portion of theVOCs from the molecule collector. As described above, at least theportion of the VOCs may be released from the molecule collector by theheat introduced within the sampling chamber by the heating element(e.g., at step 1020). The analysis device may be a massspectrometer-based device, as described above with reference to FIG. 2,or may be a THz spectrometer-based device, as described above withreference to FIG. 3. At step 1040, the method 1000 includes generating,by the analysis device, an output representative of the one or moretarget VOCs. In an aspect, the one or more target VOCs may be associatedwith one or more of Δ-9-THC, 11-hydroxy-tetrahydrocannabinol(11-OH-THC), carboxy-tetrahydrocannabinol (THC-COOH), THC metabolites,opioids (e.g., methadone and fentanyl, opioid metabolites). As describedabove, the output representative of the one or more target VOCs mayinclude information that quantitates a concentration of the one or moretarget VOCs with respect to a source of the breath sample, such as aperson providing the breath sample.

As shown above, breath analysis systems and methods in accordance withthe present disclosure may provide devices that facilitate detection ofcannabinoids and other substances from breath samples in the field. Suchsystems may be utilized by law enforcement personnel to rapidly andaccurately identify/determine whether drivers are DUIM. The ability tomake such determinations in the field greatly enhances the capabilitiesof the criminal justice field with respect to detecting and addressingthis issue. For example, previous techniques required a sample to beobtained and then sent to a lab, taking minutes or hours. This longanalysis time prevents any action from being properly taken at the sceneof the event. In contrast, utilizing breath analysis systems inaccordance with the present disclosure, local law enforcement agents canobtain conclusive evidence on scene. This application of the instrumentchallenges other fields to shift towards furthering the detection ofDUIM drivers, removing them from the roads, and enhancing the safety ofother drivers. Additionally, the breath analysis systems of the presentdisclosure may facilitate detection of other illicit drugs with rapidand portable techniques. In addition to detection in the field, theability to accurately quantitate the concentration of cannabinoidsprovided by the disclosed systems may provide the ability to develop astandard concentration used to define whether a person is DUIM.

Although embodiments of the present application and its advantages havebeen described in detail, it should be understood that various changes,substitutions and alterations can be made herein without departing fromthe spirit and scope of the invention as defined by the appended claims.Moreover, the scope of the present application is not intended to belimited to the particular embodiments of the process, machine,manufacture, composition of matter, means, methods and steps describedin the specification. As one of ordinary skill in the art will readilyappreciate from the disclosure of the present invention, processes,machines, manufacture, compositions of matter, means, methods, or steps,presently existing or later to be developed that perform substantiallythe same function or achieve substantially the same result as thecorresponding embodiments described herein may be utilized according tothe present invention. Accordingly, the appended claims are intended toinclude within their scope such processes, machines, manufacture,compositions of matter, means, methods, or steps. Moreover, the scope ofthe present application is not intended to be limited to the particularembodiments of the process, machine, manufacture, composition of matter,means, methods and steps described in the specification.

1. A system for analyzing a breath sample, the system comprising: asampling chamber; an inlet coupled to the sampling chamber andconfigured to receive a breath sample and to provide the breath sampleto the sampling chamber; a molecule collector disposed within thesampling chamber, wherein the molecule collector is configured to adhereto volatile organic compounds (VOCs) present in the breath sample; aheating element configured to introduce heat within the samplingchamber; an analysis device configured to: identify one or more targetVOCs from among the VOCs present in the sampling chamber subsequent torelease of at least a portion of the VOCs from the molecule collector,wherein at least the portion of the VOCs are released from the moleculecollector by the heat introduced within the sampling chamber by theheating element; and generate an output representative of the one ormore target VOCs.
 2. The system of claim 1, wherein the moleculecollector comprises a Carboxen® coated mesh.
 3. The system of claim 1,wherein the heating element comprises a power source coupled to themolecule collector and configured to apply a voltage to the moleculecollector to introduce the heat within the sampling chamber.
 4. Thesystem of claim 1, wherein the analysis device comprises a massspectrometer, a computing device communicatively coupled to the massspectrometer, and an output device communicatively coupled to thecomputing device, and wherein: the mass spectrometer includes: anionizer configured to ionize at least the portion of the VOCs releasedfrom the molecule collector to produce one or more ionized fragments; amass analyzer configured to separate the one or more ionized fragments;and a detector configured to identify the one or more target VOCs basedon the separated one or more ionized fragments; and the computing deviceincludes: one or more processors configured to: generate the outputrepresentative of the one or more target VOCs based on informationassociated with the one or more target VOCs identified by the detector;and display the output at the output device; and a memorycommunicatively coupled to the one or more processors.
 5. The system ofclaim 4, wherein the one or more target VOCs include Δ-9-THC,11-hydroxy-tetrahydrocannabinol (11-OH-THC),carboxy-tetrahydrocannabinol (THC-COOH), THC metabolites, opioids,opioid metabolites, or a combination thereof.
 6. The system of claim 1,wherein the sampling chamber is removable.
 7. The system of claim 1,wherein the one or more characteristics associated with the excitationof at least the portion of the VOCs comprises at least one of: anabsorbance characteristic and a fluorescent emission characteristic. 8.The system of claim 1, further comprising a disposable mouthpieceremovably coupled to a first end of the inlet, wherein a second end theinlet is coupled to the sampling chamber.
 9. The system of claim 1,further comprising a valve disposed within an air flow path between theinlet and the sampling chamber, wherein the valve is configurable to atleast a first state and a second state, the first state corresponding toan open state configured to allow the breath sample to flow into thesampling chamber and the second state corresponding to a closed stateconfigured to prevent contamination of the breath sample.
 10. The systemof claim 1, further comprising an outlet configured to release non-VOCsfrom the sampling chamber.
 11. The system of claim 1, wherein the outputrepresentative of the one or more target VOCs comprises information thatquantitates a concentration of the one or more target VOCs present inthe breath sample.
 12. The system of claim 1, further comprising asensor configured to determine whether the breath sample satisfies oneor more criterion.
 13. The system of claim 1, further comprising meansfor outputting information identifying the one or more target VOCsidentified by the analysis device.
 14. A method for analyzing a breathsample, the method comprising: receiving, at a sampling chamber, abreath sample via an inlet coupled to the sampling chamber, wherein thesampling chamber comprises a molecule collector disposed within thesampling chamber, and wherein the molecule collector is configured toadhere to volatile organic compounds (VOCs) present in the breathsample; introducing, via a heating element, heat within the samplingchamber; identifying, by an analysis device, one or more target VOCsfrom among the VOCs present in the sampling chamber subsequent torelease of at least a portion of the VOCs from the molecule collector,wherein at least the portion of the VOCs are released from the moleculecollector by the heat introduced within the sampling chamber by theheating element; and generating, by the analysis device, an outputrepresentative of the one or more target VOCs, wherein the outputrepresentative of the one or more target VOCs comprises information thatquantitates a concentration of the one or more target VOCs with respectto a source of the breath sample.
 15. The method of claim 14, whereinthe molecule collector comprises a Carboxen® coated mesh, wherein theheating element comprises a power source coupled to the moleculecollector, and wherein the method comprises applying a voltage to themolecule collector to introduce the heat within the sampling chamber.16. The method of claim 14, wherein the one or more target VOCs includeΔ-9-THC, 11-hydroxy-tetrahydrocannabinol (11-OH-THC),carboxy-tetrahydrocannabinol (THC-COOH), THC metabolites, opioids,opioid metabolites, or a combination thereof.
 17. The method of claim14, wherein the analysis device comprises a mass spectrometer, acomputing device communicatively coupled to the mass spectrometer, andan output device communicatively coupled to the computing device, andwherein the identifying the one or more target VOCs comprises: ionizing,by an ionizer of the mass spectrometer, at least the portion of the VOCsreleased from the molecule collector to produce one or more ionizedfragments; separating, by a mass analyzer of the mass spectrometer, theone or more ionized fragments; identifying, by a detector of the massspectrometer, the one or more target VOCs based on the separated one ormore ionized fragments, wherein the output representative of the one ormore target VOCs is generated, by the computing device, based oninformation associated with the one or more target VOCs identified bythe detector; and displaying the output at the output device.
 18. Themethod of claim 14, wherein the sampling chamber is removable, themethod further comprising: removing the sampling chamber; and removablyattaching a second sampling chamber, the second sampling chamberconfigured to receive a second breath sample.
 19. The method of claim18, wherein the breath sample is provided by a first person and thesecond breath sample is provided by a second person that is differentfrom the first person.
 20. A non-transitory computer-readable storagemedium storing instructions that, when executed by one or moreprocessors, cause the one or more processors to perform operations foranalyzing a breath sample, the operations comprising: activating aheating element configured to introduce heat within a sampling chambersubsequent to a breath sample being provided to the sampling chamber,wherein the sampling chamber comprises a molecule collector disposedwithin the sampling chamber, and wherein the molecule collector isconfigured to adhere to volatile organic compounds (VOCs) present in thebreath sample; identifying one or more target VOCs from among the VOCspresent in the sampling chamber subsequent to release of at least aportion of the VOCs from the molecule collector, wherein at least theportion of the VOCs are released from the molecule collector by the heatintroduced within the sampling chamber by the heating element, andwherein the one or more target VOCs include Δ-9-THC,11-hydroxy-tetrahydrocannabinol (11-OH-THC),carboxy-tetrahydrocannabinol (THC-COOH), THC metabolites, opioids,opioid metabolites, or a combination thereof; and generating an outputrepresentative of the one or more target VOCs, wherein the outputrepresentative of the one or more target VOCs comprises information thatquantitates a concentration of the one or more target VOCs with respectto a source of the breath sample.